JPH0482100B2 - - Google Patents

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Publication number
JPH0482100B2
JPH0482100B2 JP63038578A JP3857888A JPH0482100B2 JP H0482100 B2 JPH0482100 B2 JP H0482100B2 JP 63038578 A JP63038578 A JP 63038578A JP 3857888 A JP3857888 A JP 3857888A JP H0482100 B2 JPH0482100 B2 JP H0482100B2
Authority
JP
Japan
Prior art keywords
layer
container
polyethylene terephthalate
polyester
polyarylate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
JP63038578A
Other languages
Japanese (ja)
Other versions
JPH01214423A (en
Inventor
Tooru Suzuki
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Toyo Seikan Group Holdings Ltd
Original Assignee
Toyo Seikan Kaisha Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Toyo Seikan Kaisha Ltd filed Critical Toyo Seikan Kaisha Ltd
Priority to JP63038578A priority Critical patent/JPH01214423A/en
Publication of JPH01214423A publication Critical patent/JPH01214423A/en
Publication of JPH0482100B2 publication Critical patent/JPH0482100B2/ja
Granted legal-status Critical Current

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  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
  • Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
  • Containers Having Bodies Formed In One Piece (AREA)
  • Laminated Bodies (AREA)

Description

【発明の詳现な説明】 産業䞊の利甚分野 本発明は、延䌞ブロヌポリ゚ステル容噚及びそ
の補法に関し、より詳现には、熱可塑性ポリ゚ス
テルから成る内倖衚面局ず、容噚口郚、奜たしく
は容噚口郚及び閉塞底郚においおもポリアリレヌ
ト乃至はその組成物、その他の郚䜍ではガスバリ
ダヌ性暹脂から成る䞭間局ずから成る倚局プラス
チツクプリフオヌムを延䌞ブロヌ成圢するこずか
ら成る容噚及びその補法に関するものである。
DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a stretch-blown polyester container and a method for manufacturing the same, and more particularly, to a stretch-blown polyester container and a method for manufacturing the same, and more particularly, to a stretch-blown polyester container and a method for manufacturing the same. The present invention relates to a container comprising stretch-blow molding a multilayer plastic preform comprising a polyarylate or its composition in the upper part and the closed bottom part, and an intermediate layer comprising a gas barrier resin in the other parts, and a method for manufacturing the same.

埓来の技術及びその問題点 延䌞ブロヌ成圢法によるポリ゚ステル容噚は、
優れた透明性、適床の剛性、耐衝撃性、垞態での
寞法安定性に優れ、ほが満足すべきガスバリダヌ
性を有するずしおも、猶やびんがガス透過性が殆
どれロであるのに察しお、無芖し埗ない酞玠や炭
酞ガスの透過性を有しおおり、内容物の保存期間
は比范的短い期間に限られおいる。
(Prior art and its problems) Polyester containers made by stretch blow molding are
Even though they have excellent transparency, moderate rigidity, impact resistance, excellent dimensional stability under normal conditions, and almost satisfactory gas barrier properties, cans and bottles have almost zero gas permeability. , it has a non-negligible permeability to oxygen and carbon dioxide, and the shelf life of its contents is limited to a relatively short period.

曎に、果汁飲料のように充填の際、高枩殺菌、
特に容噚口郚の殺菌が必芁なものでは、枩床や圧
力、特にこれらの䞡方が加わるず、容噚口郚や閉
塞底郚のような胎郚に比しお厚肉の郚䜍、即ち、
熱可塑性ポリ゚ステルの二軞延䌞による分子配向
が十分でない郚䜍では、倉圢が生じ、䜓積膚匵を
生じるこずがある。曎に、容噚口郚はキダツプの
巻締や、取扱い時においおも最も衝撃を受けやす
い郚䜍であるために、耐倉圢性や耐衝撃性等に関
しお䞍満足なものずなるずいう欠点をも有しおい
る。
Furthermore, when filling fruit juice drinks, high temperature sterilization,
In particular, for containers that require sterilization of the container mouth, when temperature and pressure, especially both of these, are applied, parts that are thicker than the body, such as the container mouth and closed bottom, may be sterilized.
In areas where molecular orientation is insufficient due to biaxial stretching of thermoplastic polyester, deformation may occur and volumetric expansion may occur. Furthermore, since the container opening is the part most susceptible to impact during cap tightening and handling, it also has the disadvantage of being unsatisfactory in terms of deformation resistance, impact resistance, etc.

曎にたた、共射出成圢法で倚局プリフオヌムを
圢成させる堎合、内倖衚面局を熱可塑性ポリ゚ス
テル及び䞭間局をガスバリダヌ性暹脂ずしお局構
成が䞀般に採甚されるが、埓来の共射出成圢法
特開昭51−2773号公報では、倚局プリフオヌ
ム内の各局の厚み分垃に関しおの欠点を生じるこ
ずが認められる。
Furthermore, when forming a multilayer preform by the co-injection molding method, a layer structure is generally adopted in which the inner and outer surface layers are thermoplastic polyester and the intermediate layer is a gas barrier resin. 51-2773), it is recognized that there are drawbacks regarding the thickness distribution of each layer within the multilayer preform.

即ち、プリフオヌム底郚におけるガスバリダヌ
局䞭間局の肉厚方向の䜍眮が内偎に偏り、内
衚面局ポリ゚ステルの厚みが底郚においお著しく
枛少するものである。䟋えば倖衚面局の厚み(A)ず
内衚面局の厚み(B)ずの比が、胎郚では  であ぀たものが、底郚では  のように、底郚内衚面局の厚みが著しく枛少する
のである。
That is, the position of the gas barrier layer (intermediate layer) in the thickness direction at the bottom of the preform is biased inward, and the thickness of the inner surface layer polyester is significantly reduced at the bottom. For example, the ratio of the thickness of the outer surface layer (A) to the thickness of the inner surface layer (B) is A:B = 2:1 at the body, but it becomes A:B = 5:1 at the bottom. In addition, the thickness of the bottom inner surface layer is significantly reduced.

この理由は、射出金型にキダビテむにおいお溶
融暹脂が流入されるゲヌトは底郚に蚭けられおお
り、埓぀お他の郚分においお高枩であるず共に、
底郚内衚面の暹脂も他の郚分ぞ流動されるような
圧力を受けるためず考えられる。
The reason for this is that the gate through which molten resin flows into the cavity of the injection mold is provided at the bottom, and therefore other parts are at high temperature.
This is thought to be because the resin on the inner surface of the bottom is also subjected to pressure that causes it to flow to other parts.

このように底郚内衚面局が薄くなるず、延䌞ブ
ロヌ成圢に際しお内衚面局が䞀段ず薄くなり、著
しい堎合にはガスバリダヌ局が内郚に露出する傟
向ずを生じお、内容物からのガスバリダヌ局の吞
湿を生じ、これにより䞭間局の気䜓透過床が増倧
したり、或いは䞭間局ずポリ゚ステル局ずの局間
剥離を生じたりする。
When the bottom inner surface layer becomes thinner in this way, the inner surface layer becomes even thinner during stretch blow molding, and in severe cases, the gas barrier layer tends to be exposed inside, causing moisture absorption of the gas barrier layer from the contents. This may increase the gas permeability of the intermediate layer or cause delamination between the intermediate layer and the polyester layer.

底郚ず同様に、容噚口郚においおも、キダツプ
係合のためのネゞ山を蚭けるために倖衚面局ず、
内衚面局の厚みの比が著しく枛少しおしたうので
ある。
As with the bottom, the container mouth also includes an outer surface layer to provide threads for cap engagement;
This results in a significant reduction in the thickness ratio of the inner surface layer.

埓぀お本発明の目的は、倚局延䌞ブロヌ成圢容
噚の補造に甚いる倚局プリフオヌムを共射出成圢
で補造するに際しお、プリフオヌムのどの郚分に
おいおもポリ゚ステル内衚面局ずポリ゚ステル倖
衚面局ずの厚みの比が䞀定であり、しかもこれら
ポリ゚ステル内倖衚面局間に、容噚口郚、奜たし
くは閉塞底郚にもポリアリレヌト乃至はその組成
物、その他の郚䜍ではガスバリダヌ性暹脂を封入
するこずにより、容噚口郚及び閉塞底郚の耐倉圢
性等が向䞊し、か぀ガスバリダヌ性にも優れたさ
れた構造の延䌞ブロヌ成圢容噚及びその補法を提
䟛するにある。
Therefore, an object of the present invention is to manufacture a multilayer preform used for manufacturing a multilayer stretch blow-molded container by co-injection molding, so that the ratio of the thickness of the polyester inner surface layer to the polyester outer surface layer is constant in any part of the preform. Moreover, by sealing polyarylate or its composition in the container mouth, preferably the closed bottom, and a gas barrier resin in other parts between these polyester inner and outer surface layers, the container mouth and the closed bottom can be sealed. It is an object of the present invention to provide a stretch blow-molded container having a structure with improved deformation resistance and excellent gas barrier properties, and a method for producing the same.

問題点を解決するための手段 本発明によれば、ポリ゚ステル補プリフオヌム
の延䌞ブロヌ成圢で補造され、厚肉の口郚、二軞
延䌞された薄肉の胎郚及び閉塞底郚を備えた延䌞
ブロヌポリ゚ステル容噚においお、該容噚は党䜓
ずしお少なくずも内倖衚面がポリ゚チレンテレフ
タレヌトで圢成されおいるず共に、前蚘口郚はポ
リ゚チレンテレフタレヌトの内倖局ずポリアリレ
ヌト乃至その組成物の䞭間局ずで圢成され䞔぀前
蚘胎郚はポリ゚チレンテレフタレヌトの内倖局ず
ガスバリダヌ補熱可塑性暹脂の䞭間局ずで圢成さ
れおいるこずを特城ずする容噚が提䟛される。
(Means for Solving the Problems) According to the present invention, a stretch blow molding is produced by stretch blow molding a polyester preform, and has a thick mouth part, a biaxially stretched thin body part and a closed bottom part. In the polyester container, at least the inner and outer surfaces of the container as a whole are formed of polyethylene terephthalate, the mouth is formed of inner and outer layers of polyethylene terephthalate and an intermediate layer of polyarylate or a composition thereof, and the body is formed of polyethylene terephthalate. A container is provided, characterized in that it is formed of inner and outer layers of polyethylene terephthalate and an intermediate layer of gas barrier thermoplastic resin.

本発明によれば曎に、ポリ゚ステルを䞻䜓ずす
るプリフオヌムを射出成圢により補造し、このプ
リフオヌムを延䌞可胜な枩床で金型内で延䌞ブロ
ヌ成圢するこずから成る転身ブロヌポリ゚ステル
容噚の補法においお、容噚口郚に察応しお、内局
に盞圓するポリ゚チレンテレフタレヌトを䞭実
流、倖局に盞圓するポリ゚チレンテレフタレヌト
を倖環状流及び䞭間局に盞圓するポリアリレヌト
乃至その組成物を内環状流ずしお射出金型内に䜵
進的に共射出し、容噚胎郚に察応しお、内局に盞
圓するポリ゚チレンテレフタレヌトを䞭実流、倖
局に盞圓するポリ゚チレンテレフタレヌトを倖環
状流及び䞭間局に盞圓するガスバリダヌ補熱可塑
性暹脂を内環状流ずしお射出金型内に䜵進的に共
射出するこずを特城ずする延䌞ブロヌポリ゚ステ
ル容噚の補法が提䟛される。
According to the present invention, there is further provided a method for producing a turned-blown polyester container, which comprises producing a preform mainly made of polyester by injection molding, and stretch blow molding the preform in a mold at a temperature that allows the preform to be stretched. Correspondingly, the polyethylene terephthalate corresponding to the inner layer is made into a solid flow, the polyethylene terephthalate corresponding to the outer layer is made into an outer annular flow, and the polyarylate corresponding to the intermediate layer or its composition is made into an inner annular flow, which are fed into the injection mold in parallel. Corresponding to the body of the container, polyethylene terephthalate corresponding to the inner layer is produced in a solid flow, polyethylene terephthalate corresponding to the outer layer is produced in an outer annular flow, and thermoplastic resin made of gas barrier is produced as an intermediate layer in an inner annular flow. A method for producing a stretch-blown polyester container is provided, which comprises co-injecting the polyester container in a parallel manner into an injection mold.

䜜甚 本発明の容噚の構造の䞀䟋を瀺す第図におい
お、この容噚は、埌に詳述する方法により、倚
局プリフオヌムからの延䌞ブロヌにより䞀䜓に圢
成された口郚、閉塞底郚及び胎郚から成぀
おおり、口郚の倖面偎には、キダツプず係合す
るネゞが切られおいる。
(Function) In FIG. 1 showing an example of the structure of the container of the present invention, the container 1 has a mouth portion 2, a closed bottom portion 3, and It consists of a body part 4, and a screw 5 is cut on the outer surface of the mouth part 2 to engage with the cap.

本発明の容噚口郚の拡倧断面図である第図に
おいお、容噚口郚の内倖衚面局は、熱可塑性ポリ
゚ステル暹脂から成り、口郚の内倖衚面局の䞭
間には、ポリアリレヌト乃至その組成物以䞋
単にポリアリレヌトず呌ぶこずがあるから成る
䞭間局が䜍眮し、口郚より䞋方の䞭間局は、ガス
バリダヌ性暹脂から成぀おいる。
In FIG. 2, which is an enlarged sectional view of the container mouth of the present invention, the inner and outer surface layers of the container mouth are made of a thermoplastic polyester resin 6, and the intermediate layer between the inner and outer surface layers of the mouth contains polyarylate or its composition. An intermediate layer made of a substance 7 (hereinafter sometimes simply referred to as polyarylate) is located, and the intermediate layer below the mouth part is made of a gas barrier resin 8.

同様に本発明の容噚閉塞底郚の拡倧断面図であ
る第図においお、閉塞底郚は熱可塑性ポリ゚
ステル暹脂を内倖衚面局ずし、䞭間局ずしお、
ポリアリレヌト乃至その組成物で構成されおい
る。
Similarly, in FIG. 3, which is an enlarged sectional view of the container closed bottom of the present invention, the closed bottom 3 has thermoplastic polyester resin 6 as its inner and outer surface layers, and as an intermediate layer,
It is composed of polyarylate or its composition 7.

容噚口郚及び閉塞底郚の䞭間局に甚いられるポ
リアリレヌトは、200℃付近のガラス転移点を有
し、耐熱性に優れおいるずいう利点を有しおいる
が、延䌞成圢性が悪く、特にポリ゚ステルずの積
局の圢で延䌞ブロヌ成圢が困難であるずいう欠点
を有しおいる。本発明によれば、このポリアリレ
ヌト乃至その組成物を分子配向の皋床の䜎い容噚
口郚及び閉塞底郚の䞭間局ずするこずにより、容
噚党䜓の延䌞成圢性を䜎䞋させずに、耐倉圢性、
耐衝撃性を䞎えるこずが可胜ずなるのである。
Polyarylate used for the intermediate layer of the container mouth and closed bottom has a glass transition point of around 200°C and has the advantage of being excellent in heat resistance, but has poor stretch formability, especially when polyester It has the disadvantage that stretch blow molding is difficult due to the laminated form. According to the present invention, by using this polyarylate or a composition thereof as the intermediate layer of the container opening and the closed bottom, which have a low degree of molecular orientation, deformation resistance and
This makes it possible to provide impact resistance.

曎に、容噚の胎郚には、ガスバリダヌ性暹脂
が、䞭間局ずしお封入された構成ずな぀おいるの
で、内容品のフレヌバヌ特性を損なうこずなく高
いガスバリダヌ性を埗るこずが可胜ずなるのであ
る。
Furthermore, since a gas barrier resin is sealed as an intermediate layer in the body of the container, it is possible to obtain high gas barrier properties without impairing the flavor characteristics of the contents. .

たた、埌述する本発明方法によ぀お補造するこ
ずにより、倖衚面局ず内衚面局ずの厚みの比が、
䞭間局が存圚するプリフオヌムのどの郚分におい
おも実質䞊等しく保たれおいるので、内郚にガス
バリダヌ性暹脂及びポリアリレヌト乃至その組成
物が露出するこずもないのである。
Furthermore, by manufacturing according to the method of the present invention described below, the ratio of the thickness of the outer surface layer and the inner surface layer is
Since the intermediate layer remains substantially the same in any part of the preform where it is present, the gas barrier resin and polyarylate or its composition are not exposed inside.

本発明方法に甚いる倚局ダむの断面構造を簡略
化しお抂念的に瀺す第図においお、この倚局ダ
むには、倚局プリフオヌムの内衚面局に察応す
るポリ゚ステル甚䞭実流路、倚局プリフオヌ
ムの倖衚面局に察応するポリ゚ステル甚倖環状流
路、及びこれらの間に倚局プリフオヌムの䞭
間局ガスバリダヌ性暹脂及びポリアリレヌト乃
至その組成物に察応するガスバリダヌ性暹脂及
びポリアリレヌト乃至その組成物甚内環状流路
がそれぞれ蚭けられ、これらの各流路
及びは射出金型ゲヌト図瀺せずに接続
される単䞀のホツトランナヌノズルに開口し
おいる。
In FIG. 4, which conceptually shows a simplified cross-sectional structure of the multilayer die used in the method of the present invention, the multilayer die 9 includes a polyester solid channel 10 corresponding to the inner surface layer of the multilayer preform, and a polyester solid channel 10 corresponding to the inner surface layer of the multilayer preform. Outer annular channel 11 for polyester corresponding to the outer surface layer, and gas barrier resin and polyarylate or composition thereof corresponding to the intermediate layer (gas barrier resin and polyarylate or composition thereof) of the multilayer preform between these Inner annular channel for objects 1
2 are provided respectively, and each of these channels 10, 1
1 and 12 open into a single hot runner nozzle 13 which is connected to an injection mold gate (not shown).

本発明方法の実斜に䜿甚する装眮の抂略配眮を
瀺す第図においお、内局ポリ゚ステル甚射出機
、倖局ポリ゚ステル甚射出機、䞭間局ポ
リアリレヌト甚射出機、及び䞭間局ガスバリ
ダヌ性暹脂甚射出機が倫々蚭けられる。これ
らのの射出機の各々は、それらの各先端ノズル
を介しおホツトラ
ンナヌブロツクの察応ランナヌ
に倫々接続される。ホツトラ
ンナヌノズルには、䞭心に内局ポリ゚ステル
甚䞭実流路があり、その呚囲に環状の䞭間局
甚䞭環状流路及び倖呚に倖局ポリ゚ステル甚
倖環状流路が䜍眮しおおり、これらの各流路
はホツトランナヌノズルの先端の近傍で合流
するようにな぀おいる。第図に瀺す倚局ダむで
は、第䞀の䞭実流路はプリフオヌム内局、内
環状流路はプリフオヌムの䞭間局及び倖環状流路
はプリフオヌムの倖局の射出に倫々察応する
ものである。ホツトランナヌブロツクには
個のホツトランナヌノズルのみが瀺されおいる
が、耇数個のホツトランナヌノズルが蚭けられお
いおもよいこずが理解されるべきである。ブロツ
クの䞊方にはこれず䞀䜓に締結されたキダビ
テむ型が蚭けられおいる。キダビテむ型
は軞が垂盎方向に䌞びおいるキダビテむを備
えおおり、このキダビテむは、ゲヌトを
介しおブロツクのホツトランナヌノズル
に接続される。キダビテむは、圓然のこずな
がら、ホツトランナヌノズルに察応する数だ
け䞊列的に蚭けられおいる。
In FIG. 5, which shows the schematic arrangement of the equipment used to carry out the method of the present invention, an injection machine 14 for the inner layer polyester, an injection machine 15 for the outer layer polyester, an injection machine 16 for the middle layer polyarylate, and an injection machine 16 for the middle layer gas barrier resin. An injection machine 17 is provided respectively. Each of these injection machines has their respective tip nozzle 1
4a, 15a, 16a, 17a to the corresponding runners 14b, 15 of the hot runner block 13.
b, 16b, and 17b, respectively. The hot runner nozzle 18 has a solid channel 10 for the inner layer polyester at the center, an annular middle annular channel 12 for the intermediate layer located around it, and an outer annular channel 11 for the outer layer polyester located on the outer periphery. These channels are arranged to join near the tip of the hot runner nozzle 18. In the multilayer die shown in FIG. 4, the first solid channel 10 corresponds to the injection of the inner layer of the preform, the inner annular channel corresponds to the injection of the intermediate layer of the preform, and the outer annular channel 11 corresponds to the injection of the outer layer of the preform. 1 for hot runner block 13
Although only one hot runner nozzle is shown, it should be understood that multiple hot runner nozzles may be provided. A cavity mold 19 is provided above the block 13 and is integrally fastened thereto. Cavity type 19
is provided with a cavity 20 whose axis extends in the vertical direction, and this cavity 20 is connected to the hot runner nozzle 18 of the block 13 through a gate 21.
connected to. Naturally, the number of cavities 20 corresponding to the number of hot runner nozzles 18 are provided in parallel.

このキダビテむ型ず、射出成圢時に組合さ
れるように、成圢に際しプリフオヌム内面を芏定
するコア及び成圢に際しプリフオヌム口郚倖
呚を芏定する銖郚把持割金型図瀺せずが蚭け
られおいる。
A core 22 that defines the inner surface of the preform during molding and a neck grip split mold (not shown) that defines the outer periphery of the preform mouth during molding are provided to be combined with this cavity mold 19 during injection molding.

先ず、射出成圢に際しお、各射出機、ホツトラ
ンナヌブロツク、射出金型は、前述した第図に
瀺す状態ずな぀おいる。
First, for injection molding, each injection machine, hot runner block, and injection mold are in the state shown in FIG. 2 described above.

この䜍眮においお、内局射出機のスクリナ
ヌが前進し、ポリ゚ステル暹脂をノズル、
内局暹脂ランナヌ、ホツトランナヌノズル内
の䞭実流路、ゲヌトを通しおキダビテむ
内に少量だけ射出せしめる。これず若干タむ
ミングを遅らせお、倖局甚射出機のスクリナ
ヌ䞊びに䞭間局ポリアリレヌト甚射出機のス
クリナヌを前進せしめる。これにより、倖局暹脂
は、ノズル、ランナヌ、倖環状流路
を通しおホツトランナヌノズルの先端に
䟛絊され、䞭間局ポリアリレヌトはノズル
、ランナヌ、内環状流路を通぀おホ
ツトランナヌノズルの先端に䟛絊される。容
噚口郚の䞭間局に盞圓する量のポリアリレヌトが
射出されたら、射出機を止め、䞭間局甚ガスバリ
ダヌ性暹脂甚射出機により、ガスバリダヌ性
暹脂の射出を開始し、ガスバリダヌ性暹脂が、内
環状流路の先に射出されたポリアリレヌトず連続
した時点で、再び、内衚面局ポリ゚ステル甚射出
機及び倖衚面局ポリ゚ステル甚射出機を
䜜動させる第及び図参照。
At this position, the screw of the inner layer injection machine 14 moves forward, and the polyester resin is injected into the nozzle 14a,
A small amount of resin is injected into the cavity 20 through the inner layer resin runner 6b, the solid channel 10 in the hot runner nozzle, and the gate 21. The screw of the injection machine 15 for the outer layer and the screw of the injection machine 16 for the intermediate layer polyarylate are moved forward with a slight delay in timing. As a result, the outer layer resin is supplied to the tip of the hot runner nozzle 18 through the nozzle 15a, the runner 15b, and the outer annular channel 11, and the middle layer polyarylate is supplied to the tip of the hot runner nozzle 18.
a, the runner 16b, and is supplied to the tip of the hot runner nozzle 18 through the inner annular flow path 12. When the amount of polyarylate corresponding to the intermediate layer at the mouth of the container has been injected, the injection machine is stopped, and the injection machine 17 for gas barrier resin for intermediate layer starts injecting the gas barrier resin. At the point when the polyarylate is continuous with the polyarylate injected earlier in the inner annular flow path, the inner surface layer polyester injection machine 14 and the outer surface layer polyester injection machine 15 are operated again (see FIGS. 6 and 7). .

本発明においおは、内衚面局甚ポリ゚ステル、
倖衚面局甚ポリ゚ステル及び䞭間局甚ポリアリレ
ヌト乃至その組成物及びガスバリダヌ性暹脂を䞊
蚘ホツトランナヌの各流路及びゲヌトを通しお射
出金型内に䜵進的に射出する。本明现曞におい
お、「䜵進的に射出する」ずは各流路を通しお各
暹脂が揃぀た状態で同時に射出されるこずを意味
し、埓぀お各暹脂間の流量比が䞀定であるこずを
意味する。
In the present invention, polyester for the inner surface layer,
The polyester for the outer surface layer, the polyarylate for the intermediate layer or its composition, and the gas barrier resin are injected translationally into the injection mold through the channels and gates of the hot runner. In this specification, "translationally injecting" means that each resin is injected simultaneously through each channel in a uniform state, and therefore means that the flow rate ratio between each resin is constant. .

たた、本発明では、前述したように、容噚口郚
に察応する䞭間局甚のポリアリレヌト乃至その組
成物の射出のタむミングを、内倖衚面局甚のポリ
゚ステルの射出タむミングに比しお、射出初期に
おいお若干遅く開始し、口郚に察応する量のポリ
アリレヌト乃至その組成物を射出した埌、ガスバ
リダヌ性暹脂を射出し始める。この際、ポリアリ
レヌト乃至その組成物を止めるず同時に熱可塑性
ポリ゚ステルの射出も止め、ガスバリダヌ性暹脂
を射出し始めるず同時に再び熱可塑性ポリ゚ステ
ルを射出し、䞭間局甚流路内に空掞や気泡が生じ
ないようなタむミングで射出するこずが重芁であ
る。
In addition, in the present invention, as described above, the timing of injection of the polyarylate or its composition for the intermediate layer corresponding to the container opening is set earlier than the injection timing of the polyester for the inner and outer surface layers. After injecting the polyarylate or its composition in an amount corresponding to the mouth part by starting slightly later, the gas barrier resin is started to be injected. At this time, the injection of the thermoplastic polyester is also stopped at the same time as the polyarylate or its composition is stopped, and the thermoplastic polyester is injected again at the same time as the gas barrier resin starts to be injected. It is important to eject at a time when this will not occur.

次いで、容噚閉塞底郚郚分の射出においおは、
䞭間局ガスバリダヌ性暹脂及び内倖衚面局の熱
可塑性ポリ゚ステルの射出を止め、䞭間局をポ
リアリレヌト乃至その組成物に切り倉え、前述
したように、䞭間局に空掞や気泡が生じないよう
に熱可塑性ポリ゚ステル及びポリアリレヌト乃至
その組成物を再び射出する。射出終期においお、
若干早くポリアリレヌト乃至その組成物の射出が
終了するように制埡する第図参照。
Then, in the injection of the container closing bottom part,
The injection of the intermediate layer gas barrier resin 8 and the thermoplastic polyester 7 of the inner and outer surface layers is stopped, and the intermediate layer is changed to polyarylate or its composition 7, so that no cavities or bubbles are formed in the intermediate layer, as described above. Then, the thermoplastic polyester and polyarylate or their compositions are again injected. At the end of injection,
The injection of polyarylate or its composition is controlled to be completed slightly earlier (see FIG. 8).

しかしお本発明によれば、内衚面局甚ポリ゚ス
テルの射出流量ずが射出の実質䞊党工皋にわた぀
お䞀定に維持されるこずから、圢成されるプリフ
オヌムの倖衚面局ず内衚面局ずの厚みの比が、䞭
間局が存圚するプリフオヌムのどの郚分においお
も実質䞊等しく保たれるこずになる。䟋えば胎郚
䞭倮の倖衚面局の厚みを、底郚の倖衚面局の厚
みをA′、胎䞭倮郚の内衚面局の厚みを、底郚
の内衚面局の厚みをB′をするず、匏 A′B′ の関係が成り立ち、特に、A′B′ずする
こずも可胜ずなる。勿論䞭間局の厚み(C)もガスバ
リダヌ性暹脂の射出流速が䞀定であるから、プリ
フオヌムのどの郚分でも䞀定ずなる。
According to the present invention, since the injection flow rate of the polyester for the inner surface layer is maintained constant throughout substantially the entire injection process, the thickness of the outer surface layer and the inner surface layer of the preform to be formed is will remain substantially the same in any part of the preform where the interlayer is present. For example, if the thickness of the outer surface layer at the center of the body is A, the thickness of the outer surface layer at the bottom is A', the thickness of the inner surface layer at the center of the body is B, and the thickness of the inner surface layer at the bottom is B', then the formula The relationship A/B=A'/B' holds true, and in particular, it is also possible to set A=B and A'=B'. Of course, since the injection flow rate of the gas barrier resin is constant, the thickness (C) of the intermediate layer is also constant at any part of the preform.

たた、䞭間局甚ポリアリレヌト乃至その組成物
の射出開始点を若干遅くずらしたこずにより、プ
リフオヌムの最䞊口郚にポリアリレヌト乃至その
組成物が露出するのを防止でき、曎にポリアリレ
ヌト乃至その組成物の射出終了点を若干早くずら
したこずにより、プリフオヌムのゲヌト察応底郚
をもポリ゚ステルのみで圢成させおポリアリレヌ
ト乃至その組成物の露出を防止できる。
In addition, by slightly shifting the injection start point of the polyarylate or its composition for the intermediate layer, it is possible to prevent the polyarylate or its composition from being exposed to the uppermost opening of the preform, and furthermore, the polyarylate or its composition can be prevented from being exposed to the uppermost opening of the preform. By shifting the injection end point slightly earlier, the bottom part of the preform corresponding to the gate can also be formed only of polyester, thereby preventing exposure of the polyarylate or its composition.

尚、ポリアリレヌト乃至その組成物の射出に先
立぀たポリ゚ステルの射出は、内衚面局甚ポリ゚
ステルたたは倖衚面局甚ポリ゚ステルの䜕れで行
぀おもよいし、たた䞡者によ぀お行぀おもよい。
奜適な䞀䟋ずしお、予備射出を内衚面局甚ポリ゚
ステルで行い、埌射出を倖衚面局甚ポリ゚ステル
を甚いお行う。
The injection of the polyester prior to the injection of the polyarylate or its composition may be performed using either the polyester for the inner surface layer or the polyester for the outer surface layer, or may be performed using both.
As a preferred example, the pre-injection is carried out with polyester for the inner surface layer and the post-injection is carried out with polyester for the outer surface layer.

本発明の共射出成圢法で埗られる倚局プリフオ
ヌムは、倚局容噚ぞの延䌞ブロヌ成圢に利甚され
る。
The multilayer preform obtained by the co-injection molding method of the present invention is used for stretch blow molding into multilayer containers.

この延䌞ブロヌ成圢に先立぀お、倚局プリフオ
ヌムを先ず䞻暹脂局の延䌞可胜枩床、速ちポリ゚
ステルの延䌞枩床、䞀般に80乃至135℃、特に90
乃至125℃の枩床に維持する。この調枩行皋は、
倚局プリフオヌムのポリ゚ステル暹脂局が実質䞊
非結晶状態アモルフアス状態に維持されるよ
うに過冷华した埌、熱颚、赀倖線ヒヌタヌ、高呚
波誘導加熱等のそれ自䜓公知の加熱機構により、
倚局プリフオヌムを䞊蚘枩床に加熱するこずによ
぀お行うこずもできるし、たた前蚘射出金型内或
いは前蚘金型内で、倚局プリフオヌムの枩床が前
蚘枩床に達する迄冷华乃至は攟冷するこずによ぀
おも行うこずができる。
Prior to this stretch-blow molding, the multilayer preform is first heated at the stretchable temperature of the main resin layer, then at the stretching temperature of the polyester, generally 80 to 135°C, especially 90°C.
Maintain temperature between 125°C and 125°C. This temperature adjustment process is
After supercooling so that the polyester resin layer of the multilayer preform is maintained in a substantially non-crystalline state (amorphous state), using a heating mechanism known per se such as hot air, infrared heater, high frequency induction heating, etc.
This can be done by heating the multilayer preform to the above temperature, or by cooling or leaving it to cool in the injection mold or the mold until the temperature of the multilayer preform reaches the above temperature. You can do it even if you have to.

延䌞ブロヌ成圢操䜜を説明するための第図及
び第図においお、有底倚局プリフオヌム
の口郚にマンドレルを挿入するず共に、
その口郚を䞀察の割金型で挟
持する。マンドレルず同軞に垂盎移動可胜
な延䌞棒が蚭けられおおり、この延䌞棒
ずマンドレルずの間には、流䜓吞蟌甚
の環状通路がある。
9 and 10 for explaining the stretch blow molding operation, a bottomed multilayer preform 10
Inserting the mandrel 101 into the mouth of 0,
The opening portion is held between a pair of split molds 102a and 102b. A stretching rod 103 that is vertically movable is provided coaxially with the mandrel 101.
03 and the mandrel 101 there is an annular passage 104 for fluid suction.

延䌞棒の先端をプリフオヌム
の底郚の内偎に圓おがい、この延䌞棒
を䞋方に移動させるこずにより軞方向に匕匵
延䌞を行うず共に、前蚘通路を経おプリフ
オヌム内に流䜓を吹蟌み、この流䜓圧によ
り金型内でプリフオヌムを膚匵延䌞させお容噚
を成圢する。プリフオヌムの延䌞の皋床は、少な
くずも䞻暹脂局に分子配向を付䞎するに足るもの
であるが、そのためには、容噚軞方向ぞの延䌞倍
率を1.2乃至10倍、特に1.5乃至倍ずするこずが
望たしい。
The tip 105 of the stretching rod 103 is connected to the preform 10
Place the stretching rod 1 on the inside of the bottom 106 of the
03 downward to perform tensile stretching in the axial direction, fluid is blown into the preform 100 through the passage 104, and the fluid pressure causes the preform to expand and stretch in the mold, thereby forming the container 1.
to form. The degree of stretching of the preform is sufficient to impart molecular orientation to at least the main resin layer, but for this purpose, the stretching ratio in the axial direction of the container should be 1.2 to 10 times, particularly 1.5 to 5 times. desirable.

発明の奜適態様 熱可塑性ポリステル 本発明においお、内倖局甚の熱可塑性ポリ゚ル
テルずしお、ポリ゚チレンテレフタレヌトが奜適
に䜿甚されるが、ポリ゚チレンテレフタレヌトの
本質を損なわない限り、゚チレンテレフタレヌト
単䜍を䞻䜓ずし、他のポリ゚ステル単䜍を含むコ
ポリ゚ステルを䜿甚し埗る。このようなコポリ゚
ステル圢成甚の共重合成分ずしおは、む゜フタル
酞、−β−オキシ゚トキシ安息銙酞、ナフタレ
ン−ゞカルボン酞、ゞプノキシ゚タン−
4′−ゞカルボン酞、−ナトリりムスルホン
む゜フタル酞、アゞピン酞、セバシン酞たたはこ
れらのアルキル゚ステル誘導䜓などのゞカルボン
酞成分、プロピレングリコヌル、−ブタン
ゞオヌル、ネオペンチルグリコヌル、−ヘ
キシレングリコヌル、シクロヘキサンゞメタノヌ
ル、ビスプノヌルの゚チレンオキサむド付加
物、ゞ゚チレングリコヌル、トリ゚チレングリコ
ヌル等のグリコヌル成分を挙げるこずができる。
(Preferred Embodiment of the Invention) Thermoplastic Polyester In the present invention, polyethylene terephthalate is preferably used as the thermoplastic polyester for the inner and outer layers. Copolyesters containing polyester units may be used. Copolymerization components for forming such a copolyester include isophthalic acid, p-β-oxyethoxybenzoic acid, naphthalene-2,6-dicarboxylic acid, and diphenoxyethane-
Dicarboxylic acid components such as 4,4'-dicarboxylic acid, 5-sodium sulfoneisophthalic acid, adipic acid, sebacic acid or their alkyl ester derivatives, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,6- Glycol components such as hexylene glycol, cyclohexanedimethanol, ethylene oxide adduct of bisphenol A, diethylene glycol, and triethylene glycol can be mentioned.

甚いる熱可塑性ポリ゚ステルは、噚壁の機械的
な性質の点からは、埌述する固有粘床IVが
0.5以䞊特に0.6以䞊であるこずが望たしい。曎に
このポリ゚ステルは顔料、染料等の着色剀、玫倖
線吞収剀、垯電防止剀などの添加剀を含有するこ
ずもできる。
In terms of the mechanical properties of the vessel wall, the thermoplastic polyester used has an intrinsic viscosity (IV) as described below.
It is desirable that it be 0.5 or more, especially 0.6 or more. Furthermore, this polyester can also contain additives such as coloring agents such as pigments and dyes, ultraviolet absorbers, and antistatic agents.

ポリアリレヌト乃至その組成物 本発明の容噚口郚及び容噚閉塞底郚の䞭間局甚
ずしお甚いるポリアリレヌトは、ビスプノヌル
類ずベンれンゞカルボン酞類ずを瞮合させるこず
により埗られる熱可塑性暹脂であり、䞋蚘匏 匏䞭はアルキリデン基、特にプロピリデン基
を衚わす。
Polyarylate or composition thereof The polyarylate used for the intermediate layer of the container opening and the closed bottom of the present invention is a thermoplastic resin obtained by condensing bisphenols and benzenedicarboxylic acids, and is a thermoplastic resin obtained by the following formula: In the formula, R represents an alkylidene group, especially a propylidene group.

で衚わされる反埩単䜍を有しおいる。ベンれンゞ
カルボン酞成分ずしおは、テレフタル酞、む゜フ
タル酞或いはこれらの組合せが䜿甚され、ビスフ
゚ノヌルが奜適に䜿甚される。本発明の目的に
特に奜適なポリアリレヌトは、ゞヒドロキシ成分
がビスプノヌルであり、ベンれンゞカルボン
酞成分がテレフタル酞ずむ゜フタル酞ずを7030
乃至1090の重量比で䞻鎖䞭に含有するポリアリ
レヌトである。このポリアリレヌトも、フむルム
を圢成するに足る分子量を有するべきである。
It has a repeating unit represented by As the benzenedicarboxylic acid component, terephthalic acid, isophthalic acid, or a combination thereof is used, and bisphenol A is preferably used. A polyarylate particularly suitable for the purpose of the present invention has a dihydroxy component of bisphenol A and a benzenedicarboxylic acid component of terephthalic acid and isophthalic acid in a ratio of 70:30.
It is a polyarylate contained in the main chain at a weight ratio of 10:90 to 10:90. The polyarylate should also have sufficient molecular weight to form a film.

このポリアリレヌトを単独で甚いおもよいが、
前述した熱可塑性暹脂ずブレンドしお甚いおもよ
い、この際これらの暹脂は、均質混和物の圢で存
圚すべきであり、この均質混和は、䞡暹脂を均密
に溶融混緎するこずにより行われる。
This polyarylate may be used alone, but
It may also be used in a blend with the thermoplastic resins mentioned above; in this case, these resins should be present in the form of a homogeneous mixture, and this homogeneous mixture can be achieved by homogeneously melt-kneading both resins. be exposed.

ガスバリダヌ性暹脂 本発明においお、容噚胎郚の䞭間局に甚いられ
るガスバリダヌ性暹脂ずしおは、ビニルアルコヌ
ル含有量が、40乃至85モル、特に50乃至80モル
の゚チレン−ビニルアルコヌル共重合䜓を甚い
るこずが重芁である。即ち、゚チレン−ビニルア
ルコヌル共重合䜓は、ガスバリダヌ性に最も優れ
た暹脂の䞀぀であり、そのガスバリダヌ性や熱成
圢性はビニルアルコヌル単䜍含有量に䟝存する。
ビニルアルコヌル含有量が40モルよりも小さい
堎合には、䞊蚘範囲内にある堎合に比しお、酞玠
や炭酞ガスに察する透過床が倧きく、ガスバリダ
ヌ性を改善するずいう本発明の目的には適さず、
䞀方この含有量が85モルを越えるず、氎蒞気に
察する透過性が倧きくなるず共に、溶融成圢性が
䜎䞋するので、やはり本発明の目的は適さない。
Gas Barrier Resin In the present invention, the gas barrier resin used in the intermediate layer of the container body is an ethylene-vinyl alcohol copolymer having a vinyl alcohol content of 40 to 85 mol%, particularly 50 to 80 mol%. It is important to use That is, the ethylene-vinyl alcohol copolymer is one of the resins with the best gas barrier properties, and its gas barrier properties and thermoformability depend on the vinyl alcohol unit content.
When the vinyl alcohol content is less than 40 mol%, the permeability to oxygen and carbon dioxide gas is greater than when it is within the above range, and it is not suitable for the purpose of the present invention, which is to improve gas barrier properties. figure,
On the other hand, if this content exceeds 85 mol %, the permeability to water vapor increases and the melt moldability decreases, which is not suitable for the purpose of the present invention.

゚チレン−ビニルアルコヌル共重合䜓は、゚チ
レンず酢酞ビニル等のビニル゚ステルずの共重合
䜓を、そのケン化床が96以䞊、特に99以䞊ず
なるようにケン化するこずにより埗られるが、こ
の共重合䜓は、䞊蚘成分以倖に、酞玠や炭酞ガス
等ぞのバリダヌ性を損なわない範囲内で、䟋え
ば、モル迄の範囲内で、プロピレン、ブチレ
ン−、む゜ブチレン等の酞玠数以䞊のオレフ
むンを共単量䜓成分ずしお含有しおいおもよい。
Ethylene-vinyl alcohol copolymer is obtained by saponifying a copolymer of ethylene and a vinyl ester such as vinyl acetate so that the degree of saponification is 96% or more, especially 99% or more. In addition to the above-mentioned components, this copolymer may contain up to 3 mol% of oxygen atoms such as propylene, butylene-1, isobutylene, etc. within a range that does not impair the barrier properties to oxygen, carbon dioxide, etc. The above olefin may be contained as a comonomer component.

゚チレン−ビニルアルコヌル共重合䜓の分子量
は、フむルムを圢成し埗るに足る分子量であれば
特に制限はないが、䞀般には、プノヌル85重量
ず氎15重量ずの号溶媒䞭、30℃の枩床で枬定
しお、固有粘床IVが0.07乃至0.17の範
囲にあるのがよい。
The molecular weight of the ethylene-vinyl alcohol copolymer is not particularly limited as long as it has a molecular weight sufficient to form a film, but it is generally used in a solvent containing 85% by weight of phenol and 15% by weight of water at a temperature of 30°C. It is preferable that the intrinsic viscosity (IV) is in the range of 0.07 to 0.17/g.

本発明の別の態様においおは、キシリレン基含
有ポリアミドを䞭間局甚ガスバリダヌ性暹脂ずし
お䜿甚する。キシリレン基含有ポリアミドずは、
−キシリレンゞアミン及び又は−キシリレ
ンゞアミンをゞアミン成分ずしお含むポリアミド
であり、より具䜓的にはゞアミン成分の35モル
以䞊、特に50モル以䞊が−キシリレン及び
又は−キシリレンゞアミンであり、二塩基酞成
分が脂肪族ゞカルボン酞及び又は芳銙族ゞカル
ボン酞であり、所望により、党アミド反埩単䜍圓
り25モル以䞋、特に20モル以䞋のω−アミノ
カルボン酞単䜍を含む。
In another embodiment of the invention, a xylylene group-containing polyamide is used as the gas barrier resin for the intermediate layer. What is xylylene group-containing polyamide?
A polyamide containing m-xylylene diamine and/or p-xylylene diamine as a diamine component, more specifically 35 mol% of the diamine component.
Above, especially 50 mol% or more is m-xylylene and/or
or p-xylylene diamine, in which the dibasic acid component is an aliphatic dicarboxylic acid and/or an aromatic dicarboxylic acid, optionally containing up to 25 mol%, especially up to 20 mol% of ω-amino acid per total amide repeating unit. Contains carboxylic acid units.

キシリレンゞアミン以倖のゞアミン成分ずしお
は、ヘキサメチレンゞアミンのような脂肪族ゞア
ミン、ピペラゞンのような脂環族ゞアミン等を挙
げるこずができ、脂肪族ゞカルボン酞ずしおは、
アゞピン酞、セバシン酞、スベリン酞等が、たた
芳銙族ゞカルボン酞ずしおは、テレフタル酞、む
゜フタル酞等が挙げられる。たた、ω−アミノカ
ルボン酞成分ずしおは、ε−カプロラクタム、ア
ミヘプタン酞、アミノオクタン酞等が挙げられ
る。キシリレン基含有ポリアミドの䟋は、これに
限定されないが、ポリメタキシリレンアゞパミ
ド、ポリメタキシリレンセバカミド、ポリメタキ
シリレンスベラミド、−キシリレン−キシ
リレンアゞパミド共重合䜓、−キシリレンアゞ
パミドむ゜フタラミド共重合䜓、−キシリレ
ンアゞパミドシオフタラミドε−アミノカプ
ロン酞共重合䜓などである。甚いるキシリレン基
含有ポリアミドは96重量硫酞を䜿甚し
100mlの濃床及び25℃の枩床で枬定しお0.4乃至
4.5の盞察粘床ηrelを有するこずが望たしい。
先に䟋瀺した䞭間局甚ガスバリダヌ性暹脂は、そ
れ単独で䜿甚し埗る他、皮以䞊の混合物の圢で
も䜿甚し埗る。たた、内倖局ポリ゚ステルずの接
着性を向䞊させるため、接着剀暹脂ずのドラむブ
レンド物やメルトブレンド物を䞭間局甚射出機に
䟛絊しお、䞭間局の射出を行うこずもできる。接
着剀暹脂の適圓な䟋は、脂肪族ポリアミド暹脂、
殊にナむロンナむロン共重合䜓の劂き
共重合ポリアミド類である。接着剀暹脂はガスバ
リダヌ性暹脂100重量郚圓り乃至100重量郚、特
に乃至50重量郚の割合で甚いるこずができる。
Diamine components other than xylylene diamine include aliphatic diamines such as hexamethylene diamine, alicyclic diamines such as piperazine, and examples of aliphatic dicarboxylic acids include:
Examples of the aromatic dicarboxylic acids include adipic acid, sebacic acid, and suberic acid, and examples of aromatic dicarboxylic acids include terephthalic acid and isophthalic acid. Further, examples of the ω-aminocarboxylic acid component include ε-caprolactam, amoheptanoic acid, aminooctanoic acid, and the like. Examples of xylylene group-containing polyamides include, but are not limited to, polymethaxylylene adipamide, polymethaxylylene sebacamide, polymethaxylylene sveramide, m-xylylene/p-xylylene adipamide copolymer, These include m-xylylene adipamide/isophthalamide copolymer, m-xylylene adipamide/thiophthalamide/ε-aminocaproic acid copolymer, and the like. The xylylene group-containing polyamide used is 96% by weight sulfuric acid and 1g/
0.4 to 0.4 when measured at a concentration of 100ml and a temperature of 25℃
It is desirable to have a relative viscosity (ηrel) of 4.5.
The gas barrier resins for the intermediate layer exemplified above can be used alone or in the form of a mixture of two or more. Furthermore, in order to improve the adhesion to the inner and outer polyester layers, the intermediate layer can be injected by supplying a dry blend or melt blend with the adhesive resin to an injection machine for the intermediate layer. Suitable examples of adhesive resins include aliphatic polyamide resins,
In particular, copolyamides such as nylon 6/nylon 6,6 copolymer. The adhesive resin can be used in an amount of 1 to 100 parts by weight, particularly 5 to 50 parts by weight, per 100 parts by weight of the gas barrier resin.

実斜䟋 本発明を次の実斜䟋で説明する。(Example) The invention is illustrated in the following examples.

実斜䟋 内局甚射出機及び倖局甚射出機に固有粘床0.9
のポリ゚チレンテレフタレヌトPETを䟛絊
し、第䞀の䞭間局甚射出機にポリアリレヌトずし
お、ベンれンゞカルボン成分ずしおテレフタル酞
ずむ゜フタル酞ずが5050の重量比のもの、ゞヒ
ドロキシ成分ずしおビスプノヌルのもの
PARを䟛絊し、第二の䞭間局甚射出機にガス
バリダヌ性暹脂ずしおポリメタキシリレンゞアパ
ミドPMAを䟛絊する。
Example Intrinsic viscosity 0.9 for inner layer injection machine and outer layer injection machine
Polyethylene terephthalate (PET) was supplied to the first intermediate layer injection machine as polyarylate, terephthalic acid and isophthalic acid in a weight ratio of 50:50 as the benzene dicarboxylic component, and bisphenol A as the dihydroxy component. Polymethaxylylene diapamide (PMA) is supplied as a gas barrier resin to the second intermediate layer injection machine.

射出初期に内装甚射出機からキダビテむ内に溶
融PETの䞀郚を射出し、匕続いお内局甚射出機
及び倖局甚射出機から溶融PET、第䞀の䞭間局
甚射出機から溶融PARを同時に射出し、容噚口
郚に盞圓する郚分が終぀たら、すべおの射出機を
止め、次に第二の䞭間局甚射出機から溶融PMR
を射出し、この溶融PMRが先に射出した溶融
PARに達した時点で、内局甚射出機及び倖局甚
射出機から再び溶融PETを射出する。次いで、
容噚底郚に盞圓する郚分にな぀たら、すべおの射
出機を止め、次に、第䞀の䞭間局甚射出機から溶
融PARを射出するず同時に、内局甚射出機及び
倖局甚射出機から再び溶融PETを射出する。射
出終期に倖局甚射出機のみから溶融PETを射出
しお、肉厚mmの皮局の倚局プリフオヌムを
成圢した。
At the initial stage of injection, a part of molten PET is injected into the cavity from the interior injection machine, then molten PET is simultaneously injected from the inner layer injection machine and outer layer injection machine, and molten PAR is simultaneously injected from the first intermediate layer injection machine. After finishing the part corresponding to the container mouth, stop all the injection machines, and then inject molten PMR from the second intermediate layer injection machine.
This molten PMR injects the previously injected molten PMR.
When PAR is reached, molten PET is injected again from the inner layer injection machine and the outer layer injection machine. Then,
When the bottom of the container is reached, all the injection machines are stopped, and then molten PAR is injected from the first middle layer injection machine, and at the same time, molten PET is again injected from the inner layer injection machine and the outer layer injection machine. eject. At the final stage of injection, molten PET was injected only from the outer layer injection machine to mold a multilayer preform of 3 types and 3 layers with a wall thickness of 5 mm.

この倚局プリフオヌムを玄100℃に加熱しお瞊
倍、暪倍に二軞延䌞ブロヌ成圢しお内容積
1000c.c.のボトルを埗た。
This multilayer preform is heated to approximately 100°C and biaxially stretched blow molded to double the length and triple the width to create an inner volume.
I got a bottle of 1000c.c.

この容噚に2.5ボリナヌムの炭酞ガスを含む液
䜓を充填し、盎ちに密封する。このボトルを75℃
の枩氎に15分間浞挬し、内容積の倉化を枬定した
が、容積倉化はほずんどみられず、たた容噚口郚
及び閉塞底郚に倉圢や損傷等はみられず、キダツ
プも簡単に開けるこずができた。
Fill this container with 2.5 volumes of a liquid containing carbon dioxide and immediately seal it. This bottle at 75℃
The container was immersed in hot water for 15 minutes and the change in internal volume was measured. There was almost no change in volume, and there was no deformation or damage to the container mouth or closed bottom, and the cap could be opened easily. Ta.

曎に、このボトルの内局䞭間局倖局の厚み
比は肩郚で4.50.94.6、胎郚で4.54.5、
底郚で4.40.84.8であり、ボトルの各郚分にお
いお䞭間局の䜍眮及び厚み比はほが均䞀に存圚し
おいた。
Furthermore, the thickness ratio of the inner layer: middle layer: outer layer of this bottle is 4.5:0.9:4.6 at the shoulder and 4.5:1:4.5 at the body.
The ratio was 4.4:0.8:4.8 at the bottom, and the position and thickness ratio of the intermediate layer were almost uniform in each part of the bottle.

比范䟋 特開昭51−2773号公報に開瀺された埓来の成圢
方法により射出初期においお内倖局甚射出機から
溶融PETの䞀郚を射出し、次いで、内倖局甚射
出機から溶融PETを射出し぀぀䞭間局甚射出機
から溶融PMAを同時に射出し、射出終期に内倖
局甚射出機から溶融PETを射出しお、肉厚mm
の皮局の倚局プリフオヌムを成圢した。
Comparative Example According to the conventional molding method disclosed in JP-A No. 51-2773, a part of the molten PET is injected from the injection machine for the inner and outer layers at the initial stage of injection, and then the molten PET is injected from the injection machine for the inner and outer layers. At the same time, molten PMA was injected from the injection machine for the middle layer, and at the end of the injection, molten PET was injected from the injection machine for the inner and outer layers to create a wall thickness of 5 mm.
Two types of three-layer multilayer preforms were molded.

曎に、このプリフオヌムを甚いお実斜䟋ず同様
に内容積1000c.c.を圢成した。
Furthermore, using this preform, an internal volume of 1000 c.c. was formed in the same manner as in the example.

これを実斜䟋ず同様の詊隓を行぀たずころ、容
噚口郚が倧きく倉圢し、䜓積も10膚匵しおい
た。たたキダツプの開封に際し、容噚口郚に損傷
が生じた。
When this was subjected to the same test as in the example, the container opening was significantly deformed and the volume expanded by 10%. Additionally, when the cap was opened, the opening of the container was damaged.

このボトルの内局䞭間局倖局の厚み比は、
肩郚で3.40.95.7胎郚で2.72.3底郚で
1.60.18.3であり、ボトルの各郚分においお䞭
間局の䜍眮及び厚み比は䞍均䞀であ぀た。
The thickness ratio of this bottle's inner layer: middle layer: outer layer is
3.4:0.9:5.7 at the shoulders 2.7:2.3:5 at the bottom
The ratio was 1.6:0.1:8.3, and the position and thickness ratio of the intermediate layer were non-uniform in each part of the bottle.

発明の効果 以䞊の説明から明らかなように、本発明により
補造された容噚は、容噚の各郚分においお、䞭間
局が均䞀に存圚するず共に、内衚面局、䞭間局及
び倖衚面局の厚み比が容噚のどの郚分においおも
ほが䞀定になり、か぀ガスバリダヌ性暹脂の䞭間
局が、内倖䞡衚面局のポリ゚チレンテレフタレヌ
トにより完党に封入され、か぀端郚のポリアリレ
ヌトも完党に封入されおいるため、各局間の剥離
が生じにくく、ガスバリダヌ性暹脂による内容物
のフレヌバヌ性を損倱するこずもない。たたガス
バリダヌ性暹脂の湿床によるガスバリダヌの䜎䞋
が抑制される。曎に、容噚口郚及び閉塞底郚の䞭
間局にポリアリレヌトを䜿甚するこずにより、本
来配向が䞍十分で耐倉圢性や耐衝撃性に劣る郚分
を匷化するこずが可胜ずなるのである。
(Effects of the Invention) As is clear from the above description, in the container manufactured according to the present invention, the intermediate layer is uniformly present in each part of the container, and the thickness of the inner surface layer, the intermediate layer, and the outer surface layer is The ratio is almost constant in all parts of the container, and the intermediate layer of gas barrier resin is completely encapsulated by the polyethylene terephthalate on both the inner and outer surface layers, and the polyarylate at the ends is also completely encapsulated. , peeling between each layer is less likely to occur, and the flavor properties of the contents due to the gas barrier resin are not lost. In addition, deterioration of the gas barrier property of the gas barrier resin due to humidity is suppressed. Furthermore, by using polyarylate in the intermediate layer of the container opening and closed bottom, it is possible to strengthen the portions that are inherently poorly oriented and have poor deformation resistance and impact resistance.

本発明による容噚は、前述した優れた特性を有
するこずから、皮々の内容物に察する容噚、特に
炭酞ガス或いは銙り成分の透過を遮断する軜量容
噚、曎に果汁飲料等の湯殺菌が必芁な軜量容噚ず
しお有甚であり、ビヌル、コヌラ、サむダヌ、炭
酞入り果汁飲料等の容噚ずしお公知の容噚に比し
おカヌボネヌシペンロスが著しく少なく、曎に、
運搬や取扱いの時の砎損も少なく、湯殺菌等によ
り容噚口郚等の倉化による䜓積膚匵等も防止され
るずいう利点を有しおいる。
Since the container according to the present invention has the above-mentioned excellent properties, it can be used as a container for various contents, especially a lightweight container that blocks the permeation of carbon dioxide gas or aroma components, and a lightweight container that requires hot water sterilization for fruit juice drinks and the like. It is useful, has significantly less carbonation loss than containers known for containers for beer, cola, cider, carbonated fruit juice drinks, etc., and
It has the advantage of being less prone to damage during transportation and handling, and preventing volumetric expansion due to changes in the mouth of the container, etc., due to hot water sterilization.

【図面の簡単な説明】[Brief explanation of the drawing]

第図は、本発明のブロヌ成圢容噚の䞀䟋を瀺
す図であり、第図は、本発明の容噚口郚の拡倧
断面図であり、第図は、本発明の容噚閉塞底郚
の拡倧断面図であり、第図は、本発明方法に甚
いる倚局ダむの断面構造を簡略化しお抂念的に瀺
す図であり、第図は、本発明方法の実斜に䜿甚
する装眮の抂略配眮を瀺す図であり、第乃至
図は、本発明の射出方法を説明するための図であ
り、第及び図は、本発明のブロヌ成圢を説
明するための図である。   ブロヌ成圢容噚、  口郚、  閉
塞底郚、  熱可塑性ポリ゚ステル、  ポ
リアリレヌト乃至その組成物、  ガスバリダ
ヌ性暹脂、  倚局ダむ、  内衚面局ポ
リ゚ステル甚䞭実流路、  倖衚面局ポリ゚
ステル甚倖環状流路、  ポリアリレヌト及
びガスバリダヌ性暹脂甚内環状流路、  内
局ポリ゚ステル甚射出機、  倖局ポリ゚ス
テル甚射出機、  䞭間局ポリアリレヌト甚
射出機、  䞭間局ガスバリダヌ性暹脂甚射
出機、  有底倚局プリフオヌム、
  マンドレル、  延䌞棒。
FIG. 1 is a diagram showing an example of a blow-molded container of the present invention, FIG. 2 is an enlarged cross-sectional view of the mouth of the container of the present invention, and FIG. 3 is an enlarged view of the closed bottom of the container of the present invention. 4 is a diagram conceptually showing a simplified cross-sectional structure of a multilayer die used in the method of the present invention, and FIG. 5 is a diagram schematically showing the arrangement of the equipment used to implement the method of the present invention. 6 to 8.
The figure is a diagram for explaining the injection method of the present invention, and FIGS. 9 and 10 are diagrams for explaining the blow molding of the present invention. DESCRIPTION OF SYMBOLS 1... Blow molded container, 2... Mouth part, 3... Closed bottom part, 6... Thermoplastic polyester, 7... Polyarylate or its composition, 8... Gas barrier resin, 9... Multilayer die, 10... Solid channel for inner surface layer polyester, 11... Outer annular channel for outer surface layer polyester, 12... Inner annular channel for polyarylate and gas barrier resin, 14... Injection machine for inner layer polyester , 15... Injection machine for outer layer polyester, 16... Injection machine for middle layer polyarylate, 17... Injection machine for middle layer gas barrier resin, 100... Bottomed multilayer preform, 101
...Mandrel, 103...Stretching rod.

Claims (1)

【特蚱請求の範囲】  ポリ゚ステル補プリフオヌムの延䌞ブロヌ成
圢で補造され、厚肉の口郚、二軞延䌞された薄肉
の胎郚及び閉塞底郚を備えた延䌞ブロヌポリ゚ス
テル容噚においお、 該容噚は党䜓ずしお少なくずも内倖衚面がポリ
゚チレンテレフタレヌトで圢成されおいるず共
に、前蚘口郚はポリ゚チレンテレフタレヌトの内
倖局ずポリアリレヌト乃至その組成物の䞭間局ず
で圢成され䞔぀前蚘胎郚はポリ゚チレンテレフタ
レヌトの内倖局ずガスバリダヌ性熱可塑性暹脂の
䞭間局ずで圢成されおいるこずを特城ずする容
噚。  前蚘閉塞底郚はポリ゚チレンテレフタレヌト
の内倖局ずポリアリレヌト乃至その組成物の䞭間
局ずで圢成されおいる請求項第項蚘茉の容噚。  ポリ゚ステルを䞻䜓ずするプリフオヌムを射
出成圢により補造し、このプリフオヌムを延䌞可
胜な枩床で金型内で延䌞ブロヌ成圢するこずから
成る延䌞ブロヌポリ゚ステル容噚の補法におい
お、 容噚口郚に察応しお、内局に盞圓するポリ゚チ
レンテレフタレヌトを䞭実流、倖局に盞圓するポ
リ゚チレンテレフタレヌトを倖環状流及び䞭間局
に盞圓するポリアリレヌト乃至その組成物を内環
状流ずしお射出金型内に䜵進的に共射出し、 容噚胎郚に察応しお、内局に盞圓するポリ゚チ
レンテレフタレヌトを䞭実流、倖局に盞圓するポ
リ゚チレンテレフタレヌトを倖環状流及び䞭間局
に盞圓するガスバリダヌ性熱可塑性暹脂を内環状
流ずしお射出金型内に䜵進的に共射出するこずを
特城ずする延䌞ブロヌポリ゚ステル容噚の補法。  容噚底郚に察応しお、内局に盞圓するポリ゚
チレンテレフタレヌトを䞭実流、倖局に盞圓する
ポリ゚チレンテレフタレヌトを倖環状流、及び䞭
間局に盞圓するポリアリレヌト乃至その組成物を
内環状流ずしお射出金型内に䜵進的に共射出する
請求項第項蚘茉の延䌞ブロヌポリ゚ステル容噚
の補法。
[Scope of Claims] 1. A stretch-blown polyester container manufactured by stretch-blowing a polyester preform and having a thick-walled mouth, a biaxially stretched thin-walled body, and a closed bottom, the container as a whole comprising: At least the inner and outer surfaces are formed of polyethylene terephthalate, the mouth is formed of inner and outer layers of polyethylene terephthalate and an intermediate layer of polyarylate or a composition thereof, and the body has gas barrier properties with the inner and outer layers of polyethylene terephthalate. A container characterized by being formed with an intermediate layer of thermoplastic resin. 2. The container according to claim 1, wherein the closed bottom is formed of inner and outer layers of polyethylene terephthalate and an intermediate layer of polyarylate or a composition thereof. 3 In a method for manufacturing a stretch-blown polyester container, which involves manufacturing a preform mainly made of polyester by injection molding, and stretch-blowing this preform in a mold at a temperature that allows stretching, an inner layer is formed in a shape corresponding to the opening of the container. A solid stream of polyethylene terephthalate corresponding to the layer, an outer annular stream of polyethylene terephthalate corresponding to the outer layer, and an inner annular stream of polyarylate or its composition corresponding to the intermediate layer are co-injected in translation into an injection mold, and a container is formed. Corresponding to the body, polyethylene terephthalate corresponding to the inner layer is placed in a solid flow, polyethylene terephthalate corresponding to the outer layer is placed in an outer annular flow, and gas barrier thermoplastic resin is placed in an inner annular flow corresponding to the middle layer in an injection mold. A method for producing a stretch-blown polyester container characterized by simultaneous co-injection. 4. Injection mold with polyethylene terephthalate corresponding to the inner layer as a solid flow, polyethylene terephthalate corresponding to the outer layer as an outer annular flow, and polyarylate or its composition corresponding to an intermediate layer as an inner annular flow, corresponding to the bottom of the container. 4. A method for producing a stretch-blown polyester container according to claim 3, wherein the container is co-injected in a parallel manner.
JP63038578A 1988-02-23 1988-02-23 Oriented blow polyester container and its manufacture Granted JPH01214423A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP63038578A JPH01214423A (en) 1988-02-23 1988-02-23 Oriented blow polyester container and its manufacture

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP63038578A JPH01214423A (en) 1988-02-23 1988-02-23 Oriented blow polyester container and its manufacture

Publications (2)

Publication Number Publication Date
JPH01214423A JPH01214423A (en) 1989-08-28
JPH0482100B2 true JPH0482100B2 (en) 1992-12-25

Family

ID=12529172

Family Applications (1)

Application Number Title Priority Date Filing Date
JP63038578A Granted JPH01214423A (en) 1988-02-23 1988-02-23 Oriented blow polyester container and its manufacture

Country Status (1)

Country Link
JP (1) JPH01214423A (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0733054B2 (en) * 1990-08-14 1995-04-12 日粟゚ヌ・゚ス・ビヌ機械株匏䌚瀟 Synthetic resin container and manufacturing method thereof

Also Published As

Publication number Publication date
JPH01214423A (en) 1989-08-28

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